WO1994004477A1 - Hydrogenation selective de dienes et d'acetylenes dans des courants de c¿3? - Google Patents

Hydrogenation selective de dienes et d'acetylenes dans des courants de c¿3? Download PDF

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Publication number
WO1994004477A1
WO1994004477A1 PCT/US1993/007936 US9307936W WO9404477A1 WO 1994004477 A1 WO1994004477 A1 WO 1994004477A1 US 9307936 W US9307936 W US 9307936W WO 9404477 A1 WO9404477 A1 WO 9404477A1
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WO
WIPO (PCT)
Prior art keywords
propylene
distillation
column reactor
distillation column
hydrogen
Prior art date
Application number
PCT/US1993/007936
Other languages
English (en)
Inventor
Robert P. Arganbright
Original Assignee
Chemical Research & Licensing Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemical Research & Licensing Company filed Critical Chemical Research & Licensing Company
Priority to AU50882/93A priority Critical patent/AU5088293A/en
Publication of WO1994004477A1 publication Critical patent/WO1994004477A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C10G70/02—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds

Definitions

  • the present invention relates to the selective hydrogenation of di-olefins acetylenic compounds in a propylene rich stream. More particularly the invention relates to a process utilizing a supported palladium oxide catalyst as both the catalyst and as a distillation structure for the simultaneous reaction and separation of the reactants and reaction products.
  • olefinic compounds comprise ethylene, acetylene, propylene, propadiene, methyl acetylene, butenes, butadiene, etc. Many of these compounds are valuable, especially as feed stocks for chemical products. Ethylene, especially is recovered. Additionally, propylene and the butenes are valuable.
  • the olefins having more than one double bond and the acetylenic compounds (having a triple bond) have lesser uses and are detrimental to many of the chemical process in which the single double bond compounds are used, for example polymerization.
  • Hydrogenation is the reaction of hydrogen with a carbon- carbon multiple bond to "saturate" the compound. This reaction has long been known and is usually done at superatmospheric pressures and moderate temperatures using an excess of hydrogen over a metal catalyst.
  • metals known to catalyze the hydrogenation reaction are platinum, rhenium, cobalt, molybdenum, nickel, tungsten and palladium.
  • commercial forms of catalyst use supported oxides of these metals. The oxide is reduced to the active form either prior to use with a reducing agent or during use by the hydrogen in the feed.
  • These metals also catalyze other reactions, most notably dehydrogenation at elevated temperatures. Additionally they can promote the reaction of olefinic compounds with themselves or other olefins to produce dimers or oligomers as residence time is increased.
  • the present invention comprises the selective hydrogenation of acetylenic compounds and di-olefins contained within a propylene rich stream to purify the stream and obtain greater amounts of the propylene.
  • the propylene rich stream is fed to a distillation column reactor into a reaction distillation zone containing a supported palladium oxide catalyst in the form of a catalytic distillation structure. Hydrogen is provided as necessary to support the reaction and to reduce the oxide and maintain it in the hydride state.
  • the distillation column reactor is operated at a pressure such that the reaction mixture is boiling in the bed of catalyst. If desired, a bottoms stream containing any higher boiling material may be withdrawn to effectuate a complete separation. Essentially all of the acetylenic materials and propadiene are converted to propylene. Additionally, there is very little, if any, hydrogenation of the propylene to propane. There is no loss of propylene.
  • the present invention is a process for the selective hydrogenation of the di-olefins and acetylenic compounds contained within a propylene rich stream, comprising the steps of:
  • step (c) withdrawing the separated propylene from step (b) (ii) along with any propane and lighter compounds, including any unreacted hydrogen, from said distillation column reactor as overheads.
  • the process may include withdrawing any C 4 or higher boiling compounds from said distillation column reactor as bottoms.
  • reaction may be described as taking place in a mixed phase (the mixture is boiling) there is unexpectedly no oligomerization noted. This may be attributed to the fact that the propylene is boiled upward away from the catalyst continuously, reducing the residence time in the reaction distillation zone.
  • the catalytic material employed in the hydrogenation process is in a form to serve as distillation packing.
  • the catalytic material is a component of a distillation system functioning as both a catalyst and distillation packing, i.e., a packing for a distillation column having both a distillation function and a catalytic function.
  • the reaction system can be described as heterogenous since the catalyst remains a distinct entity.
  • the catalyst may be employed as palladium oxide, preferably 0.1 to 5.0 weight %, supported on an appropriate support medium such as alumina, carbon or silica, e.g., 1/8" alumina extrudates, preferably in bags as described herein or as conventional distillation packing shapes as Raschig rings, Pall rings, saddles or the like.
  • the cloth may be of any material which is not attacked by the hydrocarbon feeds or products or catalyst under the conditions of the reaction. Cotton or linen may be useful, but fiber glass cloth or TEFLON cloth is preferred.
  • a preferred catalyst system comprises a plurality of closed cloth pockets arranged and supported in the distillation column reactor by wire mesh intimately associated therewith.
  • the new catalyst structure is a catalytic distillation structure comprising flexible, semi-rigid open mesh tubular material, such as stainless steel wire mesh, filed with a particulate catalytic material said tubular material having two ends and having a length in the range of from about one-half to twice the diameter of said tubular material, a first end being sealed together along a first axis to form a first seam and a second end being sealed together along a second axis to form a second seam wherein the plane of the first seam along the axis of said tubular material and the plane of the second seam along the axis of said tubular material bisect each other at an angle of about 15 to 90°.
  • the particulate catalyst material may be a powder, small irregular chunks or fragments, small beads and the like.
  • the particular form of the catalytic material in the cloth pockets is not critical, so long as sufficient surface area is provided to allow a reasonable reaction rate.
  • the sizing of catalyst particles can be best determined for each catalytic material (since the porosity or available internal surface area will vary for different material and of course affect the activity of the catalytic material).
  • a catalyst suitable for the present process is 3.0 wt%
  • the catalyst is believed to be the hydride of palladium which is produced during operation.
  • the hydrogen rate to the reactor must be sufficient to maintain the catalyst in the active form because hydrogen is lost from the catalyst by hydrogenation.
  • the hydrogen rate must be adjusted such that it is sufficient to support the hydrogenation reaction and replace hydrogen lost from the catalyst but kept below that required for hydrogenation of propylene and to prevent flooding of the column which is understood to be the "effectuating amount of hydrogen " as that term is used herein.
  • the mole ratio of hydrogen to acetylenic compounds in the feed to the fixed bed of the present invention will be about 1.05 to 2.5 preferably 1.4 to 2.0.
  • the presence of hydrogen feed as described herein does not adversely effect the physical operation of the catalytic distillation system.
  • the present invention carries out the method in a catalyst packed column which can be appreciated to contain a vapor phase and some liquid phase as in any distillation.
  • the temperature in the reactor is determined by the boiling point of the liquid mixture present at any given pressure.
  • the temperature in the lower portions of the column will reflect the constitution of the material in that part of the column, which will be higher than the overhead; that is, at constant pressure a change in the temperature of the system indicates a change in the composition in the column.
  • To change the temperature the pressure is changed.
  • Temperature control in the reaction zone is thus effected by a change in pressure; by increasing the pressure, the temperature in the system is increased, and vice versa.
  • the distillation column reactor is operated at a pressure such that the reaction mixture is boiling in the bed of catalyst.
  • a "froth level" may maintained throughout the catalyst bed by control of the bottoms and/or overheads withdrawal rate which improves the effectiveness of the catalyst thereby decreasing the height of catalyst needed.
  • the liquid is boiling and the physical state is actually a froth having a higher density than would be normal in a packed distillation column but less than the liquid without the boiling vapors.
  • the hydrocarbon stream is rich in propylene such as a C 3 cut from the gas plant of a fluid catalytic cracking unit or a steam cracker.
  • propylene such as a C 3 cut from the gas plant of a fluid catalytic cracking unit or a steam cracker.
  • the propylene containing feed and the hydrogen may be fed to the distillation column rector separately or they may be mixed prior to feeding.
  • a mixed feed is fed below the catalyst bed or at the lower end of the bed.
  • Hydrogen alone is fed below the catalyst bed and the C 3 stream is fed below the bed up to about the lower one-third of the bed.
  • the pressure selected is that which maintains the dienes and acetylenes in the catalyst bed wile allowing the propylene and lighter to distill overhead. Any unreacted hydrogen exits overhead with the C 3 's.
  • the pilot unit used was a 1 inch laboratory column fifteen feet in height.
  • the catalyst 240 grams of 0.3 wt% PdO on 1/8 inch alumina extrudates) was placed in two inch pouches of distillation wire mesh packing to form the catalytic distillation structures described in the U.S. Serial No. 07/790,771 incorporated herein.
  • the catalytic distillation structures were loaded into the middle ten feet of the column with the lower and upper 2.5 feet filled with inert distillation packing.
  • the propylene rich feed and hydrogen were started to the column and heat added to initiate the reaction.
  • the overhead pressure was maintained at between 240 and 315 psig.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé d'hydrogénation sélective des dioléfines et des composés d'acétylène dans un courant riche en propylène, dans lequel l'hydrogénation sélective est effectuée dans un réacteur à colonne de distillation contenant un catalyseur d'hydrogénation PdO à support servant de constituant d'une structure de distillation. Essentiellement aucune hydrogénation du propylène n'a lieu, et, en outre, on ne relève que peu ou pas d'oligomérisation des composés C3.
PCT/US1993/007936 1992-08-24 1993-08-23 Hydrogenation selective de dienes et d'acetylenes dans des courants de c¿3? WO1994004477A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU50882/93A AU5088293A (en) 1992-08-24 1993-08-23 Selective hydrogenation of dienes and acetylenes in c3 streams

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US93375392A 1992-08-24 1992-08-24
US07/933,753 1992-08-24

Publications (1)

Publication Number Publication Date
WO1994004477A1 true WO1994004477A1 (fr) 1994-03-03

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Application Number Title Priority Date Filing Date
PCT/US1993/007936 WO1994004477A1 (fr) 1992-08-24 1993-08-23 Hydrogenation selective de dienes et d'acetylenes dans des courants de c¿3?

Country Status (2)

Country Link
AU (1) AU5088293A (fr)
WO (1) WO1994004477A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1009871A3 (fr) * 1994-11-03 1997-10-07 Chemical Res & Licensin Hydrogenation selective de composes fortement insatures dans des charges hydrocarbonees.
US5679241A (en) * 1995-05-17 1997-10-21 Abb Lummus Global Inc. Olefin plant recovery system employing catalytic distillation
US5859304A (en) * 1996-12-13 1999-01-12 Stone & Webster Engineering Corp. Chemical absorption process for recovering olefins from cracked gases
CN1046697C (zh) * 1996-12-25 1999-11-24 华东理工大学 一种带有丙烷循环的碳三液相选择加氢脱炔方法
US6040489A (en) * 1998-12-09 2000-03-21 Uop Llc 1,3-Butadiene separation from a crude C4 stream using catalytic extractive distillation
US6297414B1 (en) 1999-10-08 2001-10-02 Stone & Webster Process Technology, Inc. Deep selective hydrogenation process
EP1268372A1 (fr) * 2000-03-24 2003-01-02 Catalytic Distillation Technologies Elimination de methyl acetylene et propadiene (mapd) de flux d'hydrocarbures
US6734328B1 (en) 2002-11-08 2004-05-11 Catalytic Distillation Technologies Process for the selective hydrogenation of alkynes
WO2004094563A1 (fr) * 2003-03-28 2004-11-04 Exxonmobil Chemical Patents Inc. Procede pour eliminer des alcynes et/ou des dienes contenus dans un flux d'olefines
US7208646B2 (en) 2004-05-14 2007-04-24 Catalytic Distillation Technologies Selective hydrogenation of butadiene
CN102040446A (zh) * 2009-10-16 2011-05-04 中国石油化工股份有限公司 一种选择性加氢脱除mapd的催化精馏方法
CN106608805A (zh) * 2015-10-23 2017-05-03 中国石油化工股份有限公司 一种碳三馏分液相选择加氢的方法
WO2017182882A1 (fr) * 2016-04-21 2017-10-26 National Industrialization Company (Tasnee) Procédé d'hydrogénation d'alcènes et d'alcynes dans des flux de traitement d'hydrocarbures à basse pression

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB835689A (en) * 1957-12-17 1960-05-25 Bayer Ag Process for removing acetylene, methyl acetylene, and allene from hydrocarbon mixtures
US4232177A (en) * 1979-02-21 1980-11-04 Chemical Research & Licensing Company Catalytic distillation process
US4307254A (en) * 1979-02-21 1981-12-22 Chemical Research & Licensing Company Catalytic distillation process
US4336407A (en) * 1980-02-25 1982-06-22 Chemical Research & Licensing Company Catalytic distillation process
US4439350A (en) * 1982-06-21 1984-03-27 Chemical Research & Licensing Company Contact structure for use in catalytic distillation
US4443559A (en) * 1981-09-30 1984-04-17 Chemical Research & Licensing Company Catalytic distillation structure

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB835689A (en) * 1957-12-17 1960-05-25 Bayer Ag Process for removing acetylene, methyl acetylene, and allene from hydrocarbon mixtures
US4232177A (en) * 1979-02-21 1980-11-04 Chemical Research & Licensing Company Catalytic distillation process
US4307254A (en) * 1979-02-21 1981-12-22 Chemical Research & Licensing Company Catalytic distillation process
US4336407A (en) * 1980-02-25 1982-06-22 Chemical Research & Licensing Company Catalytic distillation process
US4443559A (en) * 1981-09-30 1984-04-17 Chemical Research & Licensing Company Catalytic distillation structure
US4439350A (en) * 1982-06-21 1984-03-27 Chemical Research & Licensing Company Contact structure for use in catalytic distillation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HYDROGENATION PROCESSING, March 1985, J.P. BOITIAUX et al., "Newest Hydrogenation Catalysts", pages 51-59. *

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1009871A3 (fr) * 1994-11-03 1997-10-07 Chemical Res & Licensin Hydrogenation selective de composes fortement insatures dans des charges hydrocarbonees.
US5679241A (en) * 1995-05-17 1997-10-21 Abb Lummus Global Inc. Olefin plant recovery system employing catalytic distillation
US5859304A (en) * 1996-12-13 1999-01-12 Stone & Webster Engineering Corp. Chemical absorption process for recovering olefins from cracked gases
CN1046697C (zh) * 1996-12-25 1999-11-24 华东理工大学 一种带有丙烷循环的碳三液相选择加氢脱炔方法
US6040489A (en) * 1998-12-09 2000-03-21 Uop Llc 1,3-Butadiene separation from a crude C4 stream using catalytic extractive distillation
US6297414B1 (en) 1999-10-08 2001-10-02 Stone & Webster Process Technology, Inc. Deep selective hydrogenation process
EP1268372A1 (fr) * 2000-03-24 2003-01-02 Catalytic Distillation Technologies Elimination de methyl acetylene et propadiene (mapd) de flux d'hydrocarbures
EP1268372A4 (fr) * 2000-03-24 2009-10-21 Catalytic Distillation Tech Elimination de methyl acetylene et propadiene (mapd) de flux d'hydrocarbures
US6734328B1 (en) 2002-11-08 2004-05-11 Catalytic Distillation Technologies Process for the selective hydrogenation of alkynes
US7041860B2 (en) 2002-11-08 2006-05-09 Catalytic Distillation Technologies Process for the selective hydrogenation of alkynes
US7115789B2 (en) 2003-03-28 2006-10-03 Exxon Mobil Chemical Patents Inc. Process for removal of alkynes and/or dienes from an olefin stream
US7378562B2 (en) 2003-03-28 2008-05-27 Exxonmobil Chemical Patents Inc. Process for removal of alkynes and/or dienes from an olefin stream
WO2004094563A1 (fr) * 2003-03-28 2004-11-04 Exxonmobil Chemical Patents Inc. Procede pour eliminer des alcynes et/ou des dienes contenus dans un flux d'olefines
US7208646B2 (en) 2004-05-14 2007-04-24 Catalytic Distillation Technologies Selective hydrogenation of butadiene
CN102040446A (zh) * 2009-10-16 2011-05-04 中国石油化工股份有限公司 一种选择性加氢脱除mapd的催化精馏方法
CN106608805A (zh) * 2015-10-23 2017-05-03 中国石油化工股份有限公司 一种碳三馏分液相选择加氢的方法
CN106608805B (zh) * 2015-10-23 2019-06-28 中国石油化工股份有限公司 一种碳三馏分液相选择加氢的方法
WO2017182882A1 (fr) * 2016-04-21 2017-10-26 National Industrialization Company (Tasnee) Procédé d'hydrogénation d'alcènes et d'alcynes dans des flux de traitement d'hydrocarbures à basse pression
CN108473393A (zh) * 2016-04-21 2018-08-31 塔斯尼国家工业化公司 在低压烃过程流中氢化烯烃和炔烃的方法
CN108473393B (zh) * 2016-04-21 2020-06-30 塔斯尼国家工业化公司 在低压烃过程流中氢化烯烃和炔烃的方法

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Publication number Publication date
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